CN109196081B

CN109196081B - Detergent composition for fiber products

Info

Publication number: CN109196081B
Application number: CN201780033120.3A
Authority: CN
Inventors: 尾崎贵则; 田和弘辅; 多势雄一郎
Original assignee: Kao Corp
Current assignee: Kao Corp
Priority date: 2016-05-31
Filing date: 2017-05-30
Publication date: 2021-05-11
Anticipated expiration: 2037-05-30
Also published as: US11053456B2; TWI757297B; WO2017209116A1; JP2017214570A; AU2017275180A1; EP3467080A4; US20200318034A1; EP3467080B1; SG11201809134PA; TW201800566A; CN109196081A; EP3467080A1; RU2018145760A3; RU2018145760A; AU2017275180B2; JP6944814B2; RU2747642C2

Abstract

The present invention relates to a detergent composition for fiber products, which contains the following components (a) and (B). (A) The components: an internal olefin sulfonate containing 15 to 24 carbon atoms of an internal olefin sulfonate having a sulfonic acid group at the 5-position or more; (B) the components: a nonionic surfactant having an HLB of more than 10.5 and not more than 19.

Description

Detergent composition for fiber products

Technical Field

The present invention relates to a detergent composition for fiber products, a method for cleaning fiber products, and a method for producing a detergent composition for fiber products.

Background

Conventionally, anionic surfactants, particularly alkylbenzenesulfonates, nonionic surfactants containing oxyalkylene groups having 2 to 3 carbon atoms, and olefin sulfonates, particularly internal olefin sulfonates obtained from internal olefins having double bonds not at the terminal ends of olefin chains inside thereof as raw materials have been widely used as cleaning components for household and industrial use.

Jp 2011-32456 a describes a detergent composition containing a surfactant system having low fiber adsorption properties, which is composed of a nonionic surfactant such as a specific polyoxyethylene-polyoxyalkylene alkyl ether and an anionic surfactant. As the anionic surfactant, alkyl benzene sulfonate is specifically disclosed.

Jp 2015-28123 a discloses an internal olefin sulfonate composition containing an internal olefin sulfonate having 16 carbon atoms and an internal olefin sulfonate having 18 carbon atoms at a specific ratio, which has excellent foaming properties at a specific ratio of hydroxyl compound/olefin compound.

European patent publication No. 377261 discloses a detergent composition containing an internal olefin sulfonate containing 25% or more of a β -hydroxyl group and having excellent cleaning properties. Specific examples of the detergent composition include a detergent composition containing an internal olefin sulfonate and a nonionic surfactant.

Japanese patent application laid-open No. 2003-81935 describes a detergent composition containing an internal olefin sulfonate characterized in that: the sulfonated/neutralized/hydrolyzed internal olefin is obtained by sulfonating, neutralizing and hydrolyzing an internal olefin having 8 to 30 carbon atoms, wherein the total of the proportion of double bonds existing at the 2-position is 20 to 95%, and the cis/trans ratio is 1/9 to 6/4. Formulation example 1 describes a granular detergent composition for clothing, which contains an internal olefin sulfonate and a nonionic surfactant having a polyoxyethylene group.

Japanese patent application laid-open No. 3-126793 discloses a detergent composition containing an internal olefin sulfonate derived from an internal olefin having 12 to 18 carbon atoms and a nonionic surfactant having an HLB value of 10.5 or less at a specific ratio.

Disclosure of Invention

The present invention relates to a detergent composition for textile products, a method for cleaning textile products, and a method for producing a detergent composition for textile products, in which a surfactant is less likely to be adsorbed to fibers after cleaning.

Further, the present invention relates to a detergent composition for fiber products, a method for cleaning fiber products, and a method for producing a detergent composition for fiber products, which can obtain a certain cleaning power for fiber products when using an internal olefin sulfonate obtained by using an internal olefin as a raw material.

That is, the present invention relates to a detergent composition for textile products, which contains the following components (a) and (B).

(A) The components: an internal olefin sulfonate containing 15 to 24 carbon atoms of an internal olefin sulfonate having a sulfonic acid group at the 5-position or more;

(B) the components: a nonionic surfactant having an HLB of more than 10.5 and not more than 19.

The present invention relates, in one aspect, to a detergent composition for textile products, which contains the following component (a1) and component (B).

(A1) The components: an internal olefin sulfonate obtained using, as a raw material, an internal olefin containing an internal olefin having 15 to 24 carbon atoms in which a double bond is present at the 5-position or higher;

The present invention also relates to a detergent composition for textile products, which contains the following components (a) and (B).

(A) The components: an internal olefin sulfonate which is an internal olefin sulfonate containing an internal olefin sulfonate having 15 or more and 24 or less carbon atoms, wherein the sulfonic acid group is present at the 5-position or more, and which is obtained by using, as a raw material, an internal olefin containing an internal olefin having 15 or more and 24 or less carbon atoms, wherein the double bond is present at the 5-position or more;

The present invention also relates to a method for cleaning a fiber product, wherein the fiber product is cleaned with a cleaning liquid containing the following component (a), component (B), and water, and the hardness of the cleaning liquid exceeds 0 ° dH.

In addition, the present invention relates to a method for cleaning a fiber product, wherein the fiber product is cleaned by using a cleaning liquid containing the following component (a1), component (B) and water, and the hardness of the water in the cleaning liquid exceeds 0 ° dH.

In addition, the present invention relates to a method for cleaning a fiber product, wherein the fiber product is cleaned by a cleaning liquid containing the following component (a), component (B) and water, and the hardness of the cleaning liquid exceeds 0 ° dH.

The present invention also relates to a method for producing a detergent composition for textile products, wherein the following component (a) is mixed with the following component (B).

In another aspect, the present invention relates to a method for producing a detergent composition for textile products, wherein the following component (a1) is mixed with the following component (B).

In addition, the present invention relates to a method for producing a detergent composition for textile products, wherein the following component (a) is mixed with the following component (B).

According to the present invention, a detergent composition for textile products, a method for cleaning textile products, and a method for producing a detergent composition for textile products can be provided, in which a surfactant is less likely to be adsorbed to fibers after cleaning.

Further, according to the present invention, there can be provided a detergent composition for fiber products, a method for cleaning fiber products, or a method for producing a detergent composition for fiber products, which can obtain a certain cleaning power for fiber products when an internal olefin sulfonate obtained by using an internal olefin as a raw material is used.

Detailed Description

Detergent composition for fiber products

The present inventors have found that even in an anionic surfactant present in a large amount, an internal olefin sulfonate containing a sulfonic acid group present at the 5-position or more and having 15 to 24 carbon atoms is less likely to adsorb to fibers, and the internal olefin sulfonate has 15 to 24 carbon atoms. Further, it was found that by using a nonionic surfactant having a specific HLB in combination with the above-mentioned internal olefin sulfonate, the adsorption of the surfactant to the fibers is further reduced. It is assumed that the adsorption of the surfactant to the fibers is further reduced, whereby the rinsing after cleaning of the fiber product becomes easier.

< component (A) >

The component (a) of the present invention contains an internal olefin sulfonate having 15 or more and 24 or less carbon atoms, which contains an internal olefin sulfonate having 5 or more carbon atoms and 24 or less sulfonic acid groups, and has an effect of cleaning stains attached to fibers. Further, the compound has a low adsorbability to a fiber product during cleaning.

(A) The number of carbon atoms of the internal olefin sulfonate of component (a) represents the number of carbon atoms of the internal olefin to which the sulfonate is covalently bonded. The internal olefin sulfonate of the component (a) has 15 or more, preferably 16 or more carbon atoms from the viewpoint of further improving the cleaning property of stains adhering to the fiber products, and is 24 or less, preferably 22 or less, more preferably 20 or less, and further preferably 18 or less from the viewpoint of further reducing the adsorption amount of the surfactant to the fiber products. The component (A) of the present invention is an internal olefin sulfonate having 15 to 24 carbon atoms, and the component (A) contains an internal olefin sulfonate having 15 to 24 carbon atoms in which a sulfonic acid group is present at the 5-position or higher.

From the viewpoint of further reducing the amount of adsorption of the surfactant to the fiber product, the component (a) is preferably 1 or more selected from the following components (a1) and (a2), and the mass ratio of the component (a2) to the component (a1), (a2)/(a1), is 0 or more and 1 or less.

(a1) The components: an internal olefin sulfonate containing 15 to 16 carbon atoms of an internal olefin sulfonate having a sulfonic acid group at the 5-position or more;

(a2) the components: the internal olefin sulfonate containing 17 to 24 carbon atoms, wherein the sulfonic acid group is present at the 5-position or more, is an internal olefin sulfonate containing 17 to 24 carbon atoms.

From the viewpoint of further reducing the amount of the surfactant adsorbed to the fibers during cleaning, the mass ratio of the component (a2) to the component (a1), (a2)/(a1), is 0 or more and 1 or less, preferably 0.95 or less, more preferably 0.9 or less, further preferably 0.8 or less, further more preferably 0.7 or less, further more preferably 0.6 or less, further more preferably 0.5 or less, further more preferably 0.4 or less, further more preferably 0.3 or less, further more preferably 0.2 or less, further more preferably 0.1 or less, further more preferably 0.05 or less, and further more preferably 0.

From the viewpoint of further improving the cleaning performance of stains adhering to fibers, the mass ratio (a2)/(a1) of the component (a2) to the component (a1) is 1 or less and 0 or more, preferably 0.05 or more, more preferably 0.1 or more, further preferably 0.2 or more, further more preferably 0.3 or more, further more preferably 0.4 or more, further more preferably 0.5 or more, further more preferably 0.6 or more, further more preferably 0.7 or more, further more preferably 0.8 or more, further more preferably 0.9 or more, and further more preferably 1.

In addition, the mass ratio of the component (a2) to the component (a1) (a2)/(a1) is 0 or more, preferably 0.05 or more, more preferably 0.1 or more, and 1 or less, preferably 0.95 or less, more preferably 0.9 or less, more preferably 0.8 or less, even more preferably 0.7 or less, even more preferably 0.6 or less, and even more preferably 0.5 or less, from the viewpoint of further reducing the amount of surfactant adsorbed to the fibers during cleaning and further improving the cleaning property of stains adhered to the fibers.

From the viewpoint of further reducing the amount of the surfactant adsorbed to the fiber product, the component (a) is preferably 1 or more selected from the following components (a11) and (a21), and the mass ratio (a21)/(a11) of the component (a21) to the component (a11) is 0 or more and 1 or less.

(a11) The components: an internal olefin sulfonate which is an internal olefin sulfonate having a sulfonic acid group present at the 5-position or more and is obtained from an internal olefin containing an internal olefin having 15 to 16 carbon atoms in which a double bond is present at the 5-position or more;

(a21) the components: an internal olefin sulfonate which is an internal olefin sulfonate having a sulfonic acid group at the 5-position or more and is obtained from an internal olefin containing an internal olefin having 17 to 24 carbon atoms and having a double bond at the 5-position or more.

In this case, the (a11) component may be replaced with the (a1) component, and in addition, the (a21) component may be replaced with the (a2) component, and the above-described preferable range may be applied.

The internal olefin sulfonate of the present invention is preferably a sulfonate obtained by sulfonating, neutralizing and hydrolyzing an internal olefin (an olefin having a double bond in the interior of an olefin chain) containing an internal olefin having a double bond in the 5-position or more and a carbon number of 15 to 24 as a raw material.

The internal olefin also includes a so-called α -olefin (hereinafter, also referred to as α -olefin) in which a position containing a small amount of a double bond is present at the 1-position of the carbon chain.

In addition, when internal olefins are sulfonated, β -sultone is quantitatively produced, and a part of β -sultone is changed to γ -sultone and olefin sulfonic acid, and these are further converted to hydroxyalkane sulfonate and olefin sulfonate in the neutralization and hydrolysis step (for example, j.am. oil chem. soc.69,39 (1992)). Here, the hydroxyl group of the obtained hydroxyalkanesulfonate is located inside the alkane chain, and the double bond of the olefin sulfonate is located inside the olefin chain. The obtained product is mainly a mixture of these, and a small amount of hydroxyalkanesulfonate having a hydroxyl group at the end of a carbon chain or olefin sulfonate having a double bond at the end of a carbon chain may be contained in a part of the product.

In the present specification, these respective products and their mixtures are collectively referred to as internal olefin sulfonates ((a) component). The hydroxyalkane sulfonate is referred to as internal olefin sulfonate hydroxo group (hereinafter also referred to as HAS), and the olefin sulfonate is referred to as internal olefin sulfonate hydroxo group (hereinafter also referred to as IOS).

The mass ratio of the compounds in component (a) can be measured by a high performance liquid chromatography mass spectrometer (hereinafter, abbreviated as HPLC-MS). Specifically, the mass ratio can be determined from the HPLC-MS peak area of the component (A).

Internal olefin sulfonates are known as cleaning bases. The internal olefin to be a raw material of the internal olefin sulfonate can be obtained by isomerizing 1-olefin obtained by dehydrating, for example, 1-alcohol, but it is difficult to control the position of the double bond. However, the detergent compositions containing an internal olefin sulfonate obtained by sulfonating an internal olefin produced under a different production condition and having a distribution of double bonds in different positions may have different qualities such as detergency, which is problematic for manufacturers who are required to provide detergent compositions having constant quality to users.

The present inventors have found that the content of internal olefin in which the position of double bond in internal olefin as a raw material is present at 5 or more positions is changed, and thus the detergency of a detergent composition containing the obtained internal olefin sulfonate is changed.

As the salt of the internal olefin sulfonate, an alkali metal salt, an alkaline earth metal (1/2 atom) salt, an ammonium salt or an organic ammonium salt may be mentioned. Examples of the alkali metal salt include sodium salt and potassium salt. Examples of the organic ammonium include an alkanolammonium salt having 2 to 6 carbon atoms. From the viewpoint of general versatility, the salt of the internal olefin sulfonate is preferably an alkali metal salt, and more preferably a sodium salt or a potassium salt.

According to the above-mentioned production method, it is found that the sulfonic acid group of the internal olefin sulfonate of the component (a) is present in the carbon chain of the internal olefin sulfonate, that is, in the interior of the olefin chain or the alkane chain, and that a part of the internal olefin sulfonate containing a small amount of the sulfonic acid group is present at the terminal of the carbon chain may be present. In the present invention, from the viewpoint of improving the cleaning property of stains adhering to fiber products, the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 2-position in the component (a) is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, further more preferably 25% by mass or more, further more preferably 30% by mass or more, further more preferably 35% by mass or more, further more preferably 40% by mass or more, and preferably 60% by mass or less, in the component (a).

The content of the internal olefin sulfonate having 15 to 24 carbon atoms with the sulfonic acid group being present at the 5-position in the component (a) is preferably 60% by mass or less, more preferably 57% by mass or less, even more preferably 54% by mass or less, even more preferably 50% by mass or less, even more preferably 46% by mass or less, even more preferably 42% by mass or less, even more preferably 35% by mass or less, and preferably 5% by mass or more, and even more preferably 10% by mass or more, from the viewpoint of enabling stains adhering to fiber products to be further cleaned.

The content of each compound having a different sulfonic acid group position in the component (A) can be measured by HPLC-MS. The content of each compound having a different sulfonic acid group position in the present specification is determined as a mass ratio based on the HPLC-MS peak area of the compound having a sulfonic acid group at each position in the whole HAS bodies of the component (a). Here, HAS is a hydroxyl group of hydroxyalkanesulfonate, i.e., internal olefin sulfonate, in a compound produced by sulfonation of internal olefin sulfonic acid.

The content of the olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 1-position in the component (a) is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 3% by mass or less in the component (a), and is preferably 0.01% by mass or more from the viewpoints of reduction in production cost and improvement in productivity, from the viewpoint that the cleanability of stains adhering to fiber products can be further improved even when the temperature of water used for cleaning is low, such as 0 ℃ to 15 ℃.

The position of the sulfonic acid group of these compounds is a position on the olefin chain or the alkane chain.

In the present invention, the internal olefin sulfonate having 15 or more and 24 or less carbon atoms in which a sulfonic acid group is present at the 5-position refers to a sulfonate having 15 or more and 24 or less carbon atoms in which a sulfonic acid group is present at the 5-position in the HAS body. The same applies to olefin sulfonates having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 1-or 2-position.

The internal olefin sulfonate may be a mixture of a hydroxyl radical and an olefin. (A) The mass ratio of the content of the olefin body of the internal olefin sulfonate to the content of the hydroxyl group of the internal olefin sulfonate (olefin body/hydroxyl group) in the component (a) may be 0/100 or more, further 5/95 or more, 50/50 or less, further 40/60 or less, further 30/70 or less, further 25/75 or less.

(A) The mass ratio of the content of the hydroxyl group of the internal olefin sulfonate to the content of the olefin body of the internal olefin sulfonate in the component (a) can be determined by separating the hydroxyl group and the olefin body from the component (a) or the obtained surfactant composition by High Performance Liquid Chromatography (HPLC), and identifying the separated components by Mass Spectrometry (MS), and calculating the respective ratios from the HPLC-MS peak areas.

(A) Component (b) can be produced by sulfonating, neutralizing and hydrolyzing an internal olefin having 15 to 24 carbon atoms as a raw material. The sulfonation may be performed by reacting 1.0 to 1.2 moles of sulfur trioxide gas with 1 mole of an internal olefin. The reaction temperature may be 20 to 40 ℃.

The neutralization can be carried out, for example, by reacting 1.0 to 1.5 molar times of an alkaline aqueous solution such as sodium hydroxide, ammonia, or 2-aminoethanol with respect to the theoretical amount of the sulfonic acid group. The hydrolysis reaction may be carried out, for example, in the presence of water at 90 to 200 ℃ for 30 minutes to 3 hours. These reactions can be carried out continuously. After the reaction is completed, purification may be performed by extraction, washing, or the like.

In the production of the internal olefin sulfonate (a), the raw material internal olefin having a distribution of carbon atoms of 15 to 24 carbon atoms may be used to perform sulfonation, neutralization and hydrolysis, the raw material internal olefin having a single carbon atom may be used to perform sulfonation, neutralization and hydrolysis, or a plurality of internal olefin sulfonates having different carbon atoms, which are produced in advance, may be mixed as necessary.

In the present invention, as described above, the internal olefin means an olefin having a double bond in the interior of an olefin chain. (A) The internal olefin of component (A) has 15 to 24 carbon atoms. (A) The internal olefin used as the component (C) may be used alone in 1 kind or in combination of 2 or more kinds.

The total content of the olefins having a double bond in the olefin at the 1-position in the raw material, so-called α -olefins, is preferably 10% by mass or less, more preferably 7% by mass or less, even more preferably 5% by mass or less, even more preferably 3% by mass or less, and is preferably 0.01% by mass or more from the viewpoint of reduction in production cost and improvement in productivity, from the viewpoint of further reducing the amount of the surfactant adsorbed to the fibers.

From the viewpoint of further improving the cleanability of stains adhering to fibers, the content of the olefin having a double bond in the olefin in the raw material present at the 5-position or more is preferably 60% by mass or less, more preferably 57% by mass or less, further preferably 54% by mass or less, further more preferably 50% by mass or less, further more preferably 46% by mass or less, further more preferably 42% by mass or less, and further more preferably 35% by mass or less, and from the viewpoint of further reducing the amount of the surfactant adsorbed to the fibers after cleaning, it is preferably 10% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more, further more preferably 20% by mass or more, and further more preferably 25% by mass or more. The maximum value of the position of the double bond in the olefin in the raw material differs depending on the number of carbon atoms.

The distribution of double bonds in the olefin in the raw material can be measured, for example, by a gas chromatography mass spectrometer (hereinafter abbreviated as GC-MS). Specifically, each component having a different carbon chain length and double bond position can be accurately separated by a gas chromatograph (hereinafter abbreviated as GC), and the double bond position can be identified by passing the separated component through a mass spectrometer (hereinafter abbreviated as MS), and the ratio can be determined from the GC peak area.

< ingredient (B) >

(B) The component (B) is a nonionic surfactant having an HLB of more than 10.5 and not more than 19. The preferable component (B) is a nonionic surfactant containing a polyoxyethylene group and having an HLB of more than 10.5 and 19 or less. From the viewpoint of further reducing the amount of adsorption of the surfactant to the fiber product after cleaning, the HLB of the component (B) blended in the present invention is preferably 11 or more, more preferably 12 or more, further preferably 12.5 or more, further more preferably 13 or more, further more preferably 14 or more, further more preferably 15 or more, further more preferably 16 or more, and 19 or less.

With respect to the value of HLB of the nonionic surfactant in the present invention, HLB of a nonionic surfactant containing a polyoxyethylene group means HLB calculated by the following formula. The average molecular weight of the polyoxyethylene group means an average molecular weight calculated from the average number of moles of addition when the number of moles of addition of the oxyethylene group has a distribution. The average molecular weight of the component (B) is calculated from the average molecular weight when the hydrophobic group such as a hydrocarbon group has a distribution or when the number of moles of polyoxyethylene groups added has a distribution.

HLB [ (average molecular weight of polyoxyethylene group)/[ (average molecular weight of B) component ] ] × 20

In the following, specific nonionic surfactants are exemplified, and the above oxyethylene group may be referred to as an ethyleneoxy group.

In the present invention, the HLB of the nonionic surfactant is a value measured by the method of Korea et al, which is described in Journal of Colloid and Interface Science, Vol.107.No.1, 9.1985, in the case where the nonionic surfactant does not contain a polyoxyethylene group. In this document, it is based on a specific temperature (T)_HLB) A method for measuring HLB, which is a linear relationship with the number of HLB numbers obtained by Griffin.

(B) The component (b) is preferably a nonionic surfactant having an HLB of more than 10.5 and 19 or less and represented by the following general formula (b 1).

R¹(CO)_mO-(A¹O)_n-R² (b1)

[ in the formula, R¹Is an aliphatic hydrocarbon group having 9 to 18 carbon atoms, R²Is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, A¹The O group is 1 or more selected from the group consisting of an ethyleneoxy group and a propyleneoxy group, and n is an average addition mole number and is a number of 6 to 50.]

In the general formula (b1), R¹Is an aliphatic hydrocarbon group having 9 to 16 carbon atoms. R¹The more the number of carbon atoms (b) is, the lower the HLB value is, and the less the number of carbon atoms is, the higher the HLB value is. From the viewpoint that the adsorption amount of the surfactant to the fibers after cleaning can be further reduced, R¹The number of carbon atoms of (a) is preferably 12 or more, more preferably 12.5 or more, and further preferably 13.0 or more, and is 16 or less, preferably 15 or less, from the viewpoint of easier removal of stains attached to fibers. As R¹The aliphatic hydrocarbon group of (3) is preferably a group selected from an aliphatic alkyl group and an aliphatic alkenyl group. Further, R¹The number of carbon atoms of (a) may be an average number of carbon atoms.

In the general formula (b1), A¹The O group is at least 1 selected from the group consisting of an ethyleneoxy group and a propyleneoxy group. When the compound contains an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group may be bonded in a block type or a random type. From the viewpoint that the adsorption amount of the surfactant to the fiber product after cleaning can be further reduced, A¹The O group is preferably a group containing an ethyleneoxy group. A. the¹The higher the proportion of ethyleneoxy groups in the O group, the higher the HLB value.

In the general formula (b1), n is an average molar number of addition and is a number of 6 to 50. The larger the number of n, the higher the HLB value, and the smaller the number of n, the lower the HLB value. From the viewpoint of further reducing the amount of adsorption of the surfactant to the fiber product after cleaning, n is 6 or more, preferably 6.5 or more, more preferably 7 or more, further preferably 8 or more, further more preferably 9 or more, further more preferably 10 or more, further more preferably 12 or more, and from the viewpoint of the cleanability of stains attached to the fibers, n is 50 or less, preferably 45 or less, more preferably 40 or less, further preferably 35 or less, further more preferably 26 or less, further more preferably 24 or less.

< composition et al >

From the viewpoint of further improving the cleaning performance per unit mass of the detergent composition for fiber products in cleaning fibers, the total content of the component (a) and the content of the component (B) in the detergent composition for fiber products of the present invention is preferably 4 mass% or more, more preferably 5 mass% or more, further preferably 6 mass% or more, further more preferably 7 mass% or more, further more preferably 8 mass% or more, further more preferably 9 mass% or more, and from the viewpoint of blending cost, preferably 70 mass% or less, more preferably 60 mass% or less, further preferably 50 mass% or less.

The content of the component (a) contained in the fiber-cleaning composition is calculated based on the counter ion assumed to be sodium ion. That is, the content in terms of sodium salt.

In the fiber-use detergent composition of the present invention, from the viewpoint of further improving the cleaning performance of fiber-attached stains per unit mass of the fiber-use detergent composition, from the viewpoint of being able to further reduce the amount of the surfactant adsorbed to the fiber, or from the viewpoint of maintaining the cleaning power of the fiber-attached stains at a constant level even if the content of the internal olefin having a double bond position of 5 or more in the internal olefin as the raw material of the component (a) is changed, the mass ratio of the content of the component (B) to the content of the component (a), (B)/(a), exceeds 0.05 or more, preferably 0.08 or more, more preferably 0.1 or more, more preferably 0.15 or more, more preferably 0.2 or more, more preferably 0.25 or more, more preferably 0.3 or more, more preferably 0.35 or more, more preferably 0.40 or more, and preferably 9 or less, more preferably 8 or less, more preferably 7 or less, more preferably 6 or less, and more preferably 5 or less.

The total content of the component (a) and the component (B) in the total surfactant in the detergent composition for textile products of the present invention is preferably 60 mass% or more and 100 mass% or less.

As examples of the surfactant other than the components (a) and (B), for example, the component (C) described in any of the components described later can be used. (C) The mass when the component is an anionic surfactant means the mass obtained by replacing a counter ion with a sodium ion. When the component (C) is a cationic surfactant, the mass of the compound indicates that the counter ion is replaced by a chloride ion.

In the total amount of the surfactant in the detergent composition for textile products, the total amount of the component (a) and the component (B) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, further more preferably 90% by mass or more, further more preferably 95% by mass or more, and further may be 100% by mass, from the viewpoint of further reducing the amount of the surfactant adsorbed in the textile products after cleaning.

< fiber >

The fibers constituting the textile product cleaned with the detergent composition for textile product of the present invention may be either hydrophobic fibers or hydrophilic fibers. Examples of the hydrophobic fibers include: examples of the fibers include protein fibers (e.g., casein fibers and Promix), polyamide fibers (e.g., nylon), polyester fibers (e.g., polyester), polyacrylonitrile fibers (e.g., acrylic acid), polyvinyl alcohol fibers (e.g., vinylon), polyvinyl chloride fibers (e.g., polyvinyl chloride), polyvinylidene chloride fibers (e.g., vinylidene chloride), polyolefin fibers (e.g., polyethylene and polypropylene), polyurethane fibers (e.g., polyurethane), polyvinyl chloride/polyvinyl alcohol co-polymer fibers (e.g., Polychlal), polyalkylene paraben fibers (e.g., benzoate), polyvinyl fluoride fibers (e.g., polytetrafluoroethylene), glass fibers, carbon fibers, alumina fibers, silicon carbide fibers, rock fibers (rock fibers), slag fibers (slag fibers), and metal fibers (gold, silver, and steel fibers). Examples of the hydrophilic fiber include: examples of the fibers include, but are not limited to, wool fibers (cotton, kapok, etc.), bast fibers (hemp, flax, ramie, hemp, jute, etc.), vein fibers (abaca, sisal, etc.), coconut fibers, rush, straw, animal hair fibers (wool, mohair, kesle, camel hair, alpaca hair, Vicuna hair (Vicuna), angora rabbit hair, etc.), silk fibers (silk, tussah), feathers, cellulose fibers (rayon, high wet modulus viscose (polynosic), cuprammonium fibers, acetate fibers, etc.), and the like.

The fibers are preferably cotton fiber-containing fiber products from the viewpoint that the detergent composition for fiber products of the present invention can more easily and reliably exhibit the effect of reducing the amount of the surfactant adsorbed on the fibers after cleaning, compared to conventionally known detergent compositions.

< fiber product >

In the present invention, the textile product refers to a fabric such as a woven fabric, a knitted fabric, or a nonwoven fabric using the above-mentioned hydrophobic fibers or hydrophilic fibers, and a product such as an undershirt, a T-shirt, a Y-shirt, a cover, casual pants, a hat, a handkerchief, a towel, knitwear, socks, underwear, and tights obtained using the same. The fiber product is preferably a fiber product containing cotton fibers, from the viewpoint of more easily and reliably feeling the softness of the fibers after cleaning with the detergent composition for fiber products of the present invention. From the viewpoint of further improving the flexibility of the fiber, the content of the cotton fiber in the fiber product is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, further more preferably 20% by mass or more, and further more preferably 100% by mass.

< (C) component: (A) surfactant other than component (A) >

The detergent composition for textile products of the present invention may use a surfactant other than the component (a) as the component (C) within a range not to impair the effects of the present invention. The component (C) includes 1 or more anionic surfactants selected from the following components (C1), (C2), (C3) and (C4). Further, as the other component (C), a nonionic surfactant having a hydroxyl group or a polyoxyalkylene may be mentioned as the component (C5).

(c1) The components: alkyl or alkenyl sulfates

(c2) The components: polyoxyalkylene alkyl ether sulfate or polyoxyalkylene alkenyl ether sulfate

(c3) The components: anionic surfactant having sulfonate group (except for component (A))

(c4) The components: fatty acids or salts thereof

More specifically, the component (c1) may be 1 or more anionic surfactants selected from alkyl sulfate salts in which the alkyl group has 10 to 18 carbon atoms and alkenyl sulfate salts in which the alkenyl group has 10 to 18 carbon atoms. From the viewpoint of improving the cleaning property, the component (c1) is preferably 1 or more anionic surfactants selected from alkyl sulfates in which the number of carbon atoms of the alkyl group is 12 to 14 inclusive, and more preferably 1 or more anionic surfactants selected from sodium alkyl sulfates in which the number of carbon atoms of the alkyl group is 12 to 14 inclusive.

More specifically, the component (c2) includes 1 or more anionic surfactants selected from polyoxyalkylene alkyl sulfate salts in which the alkyl group has 10 to 18 carbon atoms and the average number of moles of alkylene oxide added is 1 to 3, and polyoxyalkylene alkenyl ether sulfate salts in which the alkenyl group has 10 to 18 carbon atoms and the average number of moles of alkylene oxide added is 1 to 3. From the viewpoint of improving the cleaning property, the component (c2) is preferably a polyoxyethylene alkyl sulfate salt in which the average molar number of addition of ethylene oxide is 1 or more and 2.2 or less, more preferably a polyoxyethylene alkyl sulfate salt in which the number of carbon atoms of the alkyl group is 12 or more and 14 or less and the average molar number of addition of ethylene oxide is 1 or more and 2.2 or less, and still more preferably a sodium salt thereof.

The anionic surfactant having a sulfonate group as the component (c3) means an anionic surfactant having a sulfonate as a hydrophilic group (except for the component (a)).

More specifically, the component (c3) includes 1 or more anionic surfactants selected from alkylbenzenesulfonates having an alkyl group with 10 or more carbon atoms and 18 or less, alkenylbenzenesulfonates having an alkenyl group with 10 or more carbon atoms and 18 or less, alkanesulfonates having an alkyl group with 10 or more carbon atoms and 18 or less, α -olefinsulfonate having an α -olefin portion with 10 or more carbon atoms and 18 or less, α -sulfofatty acid salts having a fatty acid portion with 10 or more carbon atoms and 18 or less, α -sulfofatty acid lower alkyl ester salts having an ester portion with 1 or more carbon atoms and 5 or less, and internal olefinsulfonates having 12 or more carbon atoms and 14 or less. From the viewpoint of improving the cleaning property, the component (c3) is preferably an alkylbenzenesulfonate having an alkyl group with 11 to 14 carbon atoms, more preferably a sodium alkylbenzenesulfonate having an alkyl group with 11 to 14 carbon atoms.

The fatty acid or salt thereof as the component (c4) includes fatty acids having 10 to 20 carbon atoms or salts thereof. From the viewpoint of further improving the softening effect of the fibers by the component (a), the carbon number of the component (c4) is 10 or more, preferably 12 or more, more preferably 14 or more, and 20 or less, preferably 18 or less.

The salt of the anionic surfactant of the components (c1) to (c4) is preferably an alkali metal salt, more preferably a sodium salt or a potassium salt, and still more preferably a sodium salt.

< (D) component: alkaline agent

The fiber product detergent composition of the present invention may contain an alkaline agent as the component (D) from the viewpoint of further improving the cleaning property of stains adhering to fibers. Specific examples of the alkaline agent include 1 or more kinds of inorganic alkaline agents selected from sodium carbonate, potassium carbonate, sodium sesquicarbonate and sodium hydrogencarbonate. The inorganic alkaline agent is preferably 1 or more alkaline agents selected from sodium carbonate and potassium carbonate, and more preferably sodium carbonate. In addition, as another alkaline agent, there may be mentioned an alkanolamine in which, among the groups bonded to the nitrogen atom, 1 to 3 alkanol groups having 2 to 4 carbon atoms and the balance of alkyl groups having 1 to 4 carbon atoms or hydrogen atoms are present. Among them, the alkanol group is preferably a hydroxyalkyl group, and more preferably a hydroxyethyl group. In addition to the alkanol group, a hydrogen atom or a methyl group is preferable, and a hydrogen atom is particularly preferable. As the alkanolamine, there may be mentioned: alkanolamines such as 2-aminoethanol, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, diethanolamine, N-methyldiethanolamine, and triethanolamine. In the present invention, the component (D) is preferably an alkanolamine selected from the group consisting of monoethanolamine and triethanolamine, and more preferably monoethanolamine.

< ingredient (E) >

The detergent composition for fiber products of the present invention may further contain an organic solvent having 1 or more hydroxyl groups as the component (E). Examples of the organic solvent having 1 or more hydroxyl groups include alcohols having one or more and six-membered aliphatic hydrocarbon groups having 2 or more and 6 or less carbon atoms, and examples thereof include 1 or more organic solvents selected from ethanol, 1-propanol, 2-propanol, ethylene glycol, propylene glycol, butylene glycol, 2-methyl-2, 4-pentanediol, 1, 5-pentanediol, 1, 6-hexanediol, glycerol, and 2-methyl-2, 4-pentanediol.

< water >)

The detergent composition for textile products of the present invention may contain water in order to be liquid at 4 ℃ to 40 ℃. As the water, deionized water (also referred to as ion-exchanged water) or water to which sodium hypochlorite is added in an amount of 1mg/kg to 5mg/kg of the ion-exchanged water can be used. In addition, tap water may also be used.

In the detergent composition for fibers of the present invention, the content of water is preferably 4% by mass or more, more preferably 5% by mass or more, and is preferably 85% by mass or less, more preferably 80% by mass or less.

In addition, the following components (f1) to (f7) may be blended in the liquid detergent composition for textile products of the present invention.

(f1) 0.01-10 wt% of a recontamination inhibitor such as polyacrylic acid, polymaleic acid, or carboxymethylcellulose and a dispersant

(f2) 0.01-10 wt% of bleaching agent such as hydrogen peroxide, sodium percarbonate or sodium perborate

(f3)0.01 to 10% by mass of tetraacetylethylenediamine, and bleaching activators such as bleaching activators represented by general formulae (I-2) to (I-7) of Japanese patent application laid-open No. 6-316700

(f4)0.001 mass% or more, preferably 0.01 mass% or more, more preferably 0.1 mass% or more, further preferably 0.3 mass% or more, and 2 mass% or less, preferably 1 mass% or less of 1 or more enzymes selected from the group consisting of cellulase, amylase, pectinase, protease and lipase, preferably 1 or more enzymes selected from the group consisting of amylase and protease

(f5) Fluorescent dyes of 0.001 mass% or more and 1 mass% or less, for example, fluorescent dyes commercially available as Tinopal CBS (trade name, manufactured by Ciba Speciality Chemicals inc.) or Whitex SA (trade name, manufactured by sumitomo chemical corporation)

(f6) 0.01-2% by mass of antioxidant such as butylhydroxytoluene, distyrenated cresol, sodium sulfite and sodium bisulfite

(f7) Appropriate amount of pigment, perfume, antibacterial antiseptic, and defoaming agent such as silicone.

From the viewpoint of further improving the cleaning performance of stains adhering to fibers, the pH of the detergent composition for fibers of the present invention at 20 ℃ is preferably 3 or more, more preferably 3.5 or more, and preferably 9 or less, more preferably 8 or less.

[ method of cleaning textile product ]

The method for cleaning fibers of the present invention is a method for cleaning a fiber product with a cleaning solution containing component (a), component (B) and water, and the hardness of the cleaning solution exceeds 0 ° dH.

In the method for cleaning a fiber product of the present invention, the cleaning liquid is preferably obtained by using the detergent composition for a fiber product of the present invention.

The matters described in the detergent composition for fiber products of the present invention can be suitably applied to the method for cleaning fiber products of the present invention.

The cleaning method of the fiber product of the present invention can further clean stains attached to the fiber product by the hardness of the cleaning liquid exceeding 0 ° dH. From the viewpoint of further improving the cleaning performance of stains adhering to fiber products, the hardness of the cleaning liquid is preferably 0.5 ° dH or more, more preferably 1 ° dH or more, further preferably 2 ° dH or more, further more preferably 3 ° dH or more, and is preferably 20 ° dH or less, more preferably 10 ° dH or less, further preferably 8 ° dH or less, and further more preferably 6 ° dH or less, in terms of the german hardness.

Herein, the German hardness (. degree.dH) in the present specification means that the concentrations of calcium and magnesium in water are CaCO₃Hardness as a concentration equivalent and expressed as 1mg/l (ppm) of about 0.056 ° dH (1 ° dH 17.8 ppm).

The concentrations of calcium and magnesium for obtaining the german hardness can be determined by chelate titration using disodium ethylenediaminetetraacetate.

The specific method for measuring the german hardness of water in the present specification is shown below.

Method for measuring German hardness of Water

[ reagent ]

0.01mol/l EDTA.2Na solution: 0.01mol/l aqueous solution of disodium ethylenediaminetetraacetate (titration solution, 0.01M EDTA-Na2, manufactured by SIGMA-ALDRICH Co., Ltd.)

Universal BT indicator (product name: Universal BT, Co., Ltd., Dojindo chemical research Co., Ltd.)

Ammonia buffer solution for hardness measurement (solution prepared by dissolving 67.5g of ammonium chloride in 570ml of 28 w/v% aqueous ammonia and making the total amount to 1000ml with ion-exchanged water)

[ measurement of hardness ]

(1) 20ml of water to be a sample was collected into a conical beaker using a full capacity pipette.

(2) 2ml of an ammonia buffer solution for hardness measurement was added.

(3) 0.5ml of Universal BT indicator was added. The added solution was confirmed to be purple red.

(4) While the conical beaker was sufficiently shaken and mixed, a 0.01mol/l EDTA-2 Na solution was dropped from the burette, and the end point of the titration was defined as the time point at which the water that became the sample changed to blue.

(5) The total hardness was determined from the following calculation formula.

Hardness (° dH) ═ T × 0.01 × F × 56.0774 × 100/a

T: titration amount (mL) of 0.01mol/l EDTA-2 Na solution

A: sample volume (20mL, volume of water to be a sample)

F: coefficient of 0.01mol/l EDTA-2 Na solution

The hardness of the cleaning liquid is usually more than 0 ° dH by mixing water having a hardness of more than 0 ° dH, preferably in the above range, with the component (a), the component (B), and any component, without using a component for supplementing the hardness component. Therefore, the cleaning liquid used in the present invention can be obtained by mixing water having a hardness exceeding 0 ° dH with the (a) component and the (B) component without using a component for supplementing the hardness component.

The content of the component (a) in the cleaning liquid is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 1.0% by mass or less, more preferably 0.8% by mass or less.

The content of the component (B) in the cleaning liquid is preferably 0.001 mass% or more, more preferably 0.002 mass% or more, and preferably 5.0 mass% or less, more preferably 1.0 mass% or less.

The mass ratio (B)/(a) of the component (B) to the component (a) in the cleaning liquid is preferably selected from the ranges described in the detergent composition for fiber products of the present invention.

In the total surfactant in the cleaning liquid, the total of the content of the component (a) and the content of the component (B) is 60 mass% or more, preferably 70 mass% or more, more preferably 80 mass% or more, further preferably 90 mass% or more, further more preferably 95 mass% or more, and further may be 100 mass% from the viewpoint of further reducing the amount of the surfactant adsorbed to the fiber product after cleaning.

From the viewpoint of further improving the cleaning property of stains adhering to the fibers, the temperature of the cleaning liquid is preferably 0 ℃ or higher, more preferably 3 ℃ or higher, further preferably 5 ℃ or higher, and preferably 40 ℃ or lower, more preferably 35 ℃ or lower.

From the viewpoint that the cleaning property of stains adhering to fibers can be further improved, the pH value of the cleaning liquid at 20 ℃ is preferably 3 or more, more preferably 4 or more, and preferably 10 or less, more preferably 9 or less. The pH value can be measured by the following measurement method.

< method for measuring pH >

A composite electrode for pH measurement (glass slide type manufactured by HORIBA) was connected to a pH meter (pH/ion meter F-23 manufactured by HORIBA) and then connected to a power source. Saturated aqueous potassium chloride (3.33 mol/L) was used as the pH electrode internal solution. Subsequently, the pH4.01 standard solution (phthalate standard solution), the pH6.86 standard solution (neutral phosphate standard solution), and the pH9.18 standard solution (borate standard solution) were each filled in a 100mL beaker and immersed in a thermostatic bath at 25 ℃ for 30 minutes. The pH measuring electrode was immersed in the standard solution adjusted to a constant temperature for 3 minutes, and the calibration was performed in the order of pH6.86 → pH9.18 → pH 4.01. The sample to be measured was adjusted to 25 ℃, and the electrode having the above pH was immersed in the sample to measure the pH 1 minute later.

In recent years, washing machines have been becoming larger in size, and the value of the bath ratio represented by the ratio of the mass (kg) of the laundry to the amount (liter) of the cleaning liquid, that is, the value of the amount (liter) of the cleaning liquid/the mass (kg) of the laundry (hereinafter, this ratio may be referred to as the bath ratio) tends to become smaller. When a household washing machine is used, if the bath ratio is decreased, the amount of the surfactant adsorbed to the fiber product during cleaning may increase. The method for cleaning clothing of the present invention can reduce the amount of the surfactant adsorbed on the textile during cleaning even under cleaning conditions with a low bath ratio. The bath ratio is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, further more preferably 5 or more, and preferably 45 or less, more preferably 40 or less, further preferably 30 or less, and further more preferably 20 or less, from the viewpoint of maintaining the cleaning power of stains adhering to the fiber product and reducing the amount of the surfactant adsorbed to the fiber product during cleaning.

The cleaning method of the fiber product of the invention can make the fiber more flexible even if the cleaning time is shorter. The cleaning time is preferably 1 minute or more, more preferably 2 minutes or more, and further preferably 3 minutes or more from the viewpoint of easily removing stains attached to the fibers or making the fibers more pliable, and is preferably 1 hour or less, more preferably 30 minutes or less, further preferably 20 minutes or less, and further more preferably 15 minutes or less from the viewpoint of making the fibers more pliable.

The cleaning method of the fiber product of the present invention is suitable for a rotary cleaning method. The rotary cleaning method is a cleaning method in which fibers not fixed to a rotating machine are rotated around a rotating shaft together with a cleaning liquid. The rotary cleaning method may be implemented using a rotary washing machine. Therefore, in the present invention, it is preferable to clean the fibers by using a rotary washing machine, from the viewpoint that the fibers are more flexible. Specific examples of the rotary washing machine include a drum washing machine, a pulsator washing machine, and a pulsator washing machine. These rotary washing machines may be commercially available as home-use washing machines, respectively. In recent years, drum-type washing machines have rapidly become popular in that the amount of water used for 1-time washing can be further reduced. The drum type washing machine can reduce the amount of water in particular during cleaning. The method for cleaning a textile product of the present invention is preferably a method for cleaning a textile product using a drum-type washing machine, from the viewpoint that the effects of the present invention can be further enjoyed.

< method for producing detergent composition for fiber product >

The method for producing the detergent composition for textile products of the present invention is a method for producing a detergent composition for textile products by mixing the following component (a) with the following component (B).

According to the method for producing a detergent composition for textile products of the present invention, a detergent composition for textile products can be obtained in which a surfactant is less likely to be adsorbed to fibers after cleaning.

In addition, according to the method for producing a detergent composition for a fiber product of the present invention, for example, in the internal olefin having 15 or more and 24 or less carbon atoms as a raw material, even if the content of the internal olefin having a double bond at 5-position or more is changed, a detergent composition for a fiber product capable of obtaining a certain cleaning power against stains adhering to a fiber product can be obtained.

Further, by using the component (a) in combination with the component (B), a detergent composition for textile products can be obtained in which the surfactant is less likely to be adsorbed to the fibers after cleaning.

The method for producing the detergent composition for textile products of the present invention can be applied to the matters described in the detergent composition for textile products and the method for cleaning textile products of the present invention.

(A) The component (B) is an internal olefin sulfonate having 15 to 24 carbon atoms, which contains an internal olefin sulfonate having 15 to 24 carbon atoms in which a sulfonic acid group is present at the 5-position or higher. (A) The component (B) may be an internal olefin sulfonate obtained by using, as a raw material, an internal olefin containing an internal olefin having 15 to 24 carbon atoms in which a double bond is present at the 5-position or more.

From the viewpoint of further improving the cleanability of stains adhering to fibers, the content of the olefin having a double bond in the olefin in the raw material present at the 5-position or more is preferably 60% by mass or less, more preferably 57% by mass or less, further preferably 54% by mass or less, further more preferably 50% by mass or less, further more preferably 46% by mass or less, further more preferably 42% by mass or less, and further more preferably 35% by mass or less, and from the viewpoint of further reducing the amount of the surfactant adsorbed to the fibers after cleaning, the content is preferably 10% by mass or more, more preferably 12% by mass or more, further preferably 15% by mass or more, further more preferably 20% by mass or more, and further more preferably 25% by mass or more.

The method for producing the detergent composition for textile products of the present invention may be a method in which the component (a), the component (B), and "water" as an optional component of the detergent composition for textile products described above are mixed.

From the viewpoint of further improving the cleaning performance per unit mass of the detergent composition for fiber products, the component (a) is preferably mixed so that the total content of the component (a) and the content of the component (B) in the obtained detergent composition for fiber products is preferably 4 mass% or more, more preferably 5 mass% or more, further preferably 6 mass% or more, further preferably 7 mass% or more, further more preferably 8 mass% or more, and further more preferably 9 mass% or more, and from the viewpoint of blending cost, preferably 70 mass% or less, more preferably 60 mass% or less, and further preferably 50 mass% or less.

The content of the component (a) contained in the fiber-cleaning composition is calculated based on the counter ion assumed to be sodium ion.

From the viewpoint of further improving the cleaning performance of fiber-adhering stains per unit mass of the detergent composition for fiber products, the amount of the surfactant to be adsorbed on fiber products can be further reduced, or from the viewpoint of maintaining the cleaning power of fiber-adhering stains constant even when the content of the internal olefin having a double bond position of 5 or more in the internal olefin as a raw material of the component (a) is changed in the process for producing the detergent composition for fiber products, the component (a) and the component (B) are preferably such that the mass ratio (B)/(a) of the content of the component (B) to the content of the component (a) in the obtained detergent composition for fiber products exceeds 0, preferably 0.05 or more, more preferably 0.08 or more, further preferably 0.1 or more, further more preferably 0.15 or more, More preferably 0.2 or more, still more preferably 0.25 or more, still more preferably 0.3 or more, still more preferably 0.35 or more, and still more preferably 0.40 or more, and preferably 9 or less, more preferably 8 or less, still more preferably 7 or less, still more preferably 6 or less, and still more preferably 5 or less.

(A) The component (a) and the component (B) are preferably mixed so that the total of the content of the component (a) and the content of the component (B) in the total surfactant in the obtained detergent composition for fiber products is 60 mass% or more and 100 mass% or less.

Examples of the surfactant other than the components (a) and (B) include, for example, the component (C) described in any of the above components. (C) The mass when the component is an anionic surfactant means the mass obtained by replacing a counter ion with a sodium ion. When the component (C) is a cationic surfactant, the mass of the compound indicates that the counter ion is replaced by a chloride ion.

From the viewpoint of further reducing the amount of the surfactant adsorbed to the fiber product after cleaning, the component (a) and the component (B) are preferably mixed so that the total of the content of the component (a) and the content of the component (B) in the total surfactant in the obtained detergent composition for fiber products is preferably 60 mass% or more, more preferably 70 mass% or more, further preferably 80 mass% or more, further more preferably 90 mass% or more, further more preferably 95 mass% or more, and further more preferably 100 mass%.

When the component (a), the component (B) and water are mixed, the component (a), the component (B) and water may be charged into a stirring vessel and mixed, or the mixture (1) in which two components selected from the component (a), the component (B) and water are previously mixed and the remaining components may be charged into a stirring vessel and mixed.

When the component (a), the component (B) and water are separately charged into a stirring vessel and mixed, the component (a), the component (B) and water may be sequentially charged into the stirring vessel or may be simultaneously charged. The components may be added in the whole amount at one time or in portions.

When the mixture (1) in which two components selected from the group consisting of the component (a), the component (B) and water are mixed in advance and the remaining components are put into a stirring vessel and mixed, the mixture (1) and the remaining components may be put into the stirring vessel in sequence or simultaneously. The components may be added in the whole amount at one time or in portions.

The temperature of the mixture at the time of mixing is not limited. For example, the temperature of the mixture may be 5 ℃ or higher and 70 ℃ or lower, from the viewpoint of easier mixing.

< embodiment of the present invention >

Embodiments of the present invention are exemplified below. In these embodiments, the matters described in the liquid detergent composition for textile products and the method for producing a liquid detergent composition for textile products of the present invention can be suitably applied.

< 1 > a detergent composition for fiber products, which comprises the following components (A) and (B),

< 2 > the detergent composition for fiber products as < 1 >, wherein the component (B) is a nonionic surfactant containing a polyoxyethylene group and having HLB of more than 10.5 and 19 or less.

< 3 > such as < 1 > or < 2 >, wherein the HLB of component (B) is 11 or more, preferably 12 or more, more preferably 12.5 or more, further preferably 13 or more, further more preferably 14 or more, and 19 or less.

< 4 > the detergent composition for fiber products as described in any of < 1 > to < 3 >, wherein the component (B) is a nonionic surfactant represented by the following general formula (B1).

R¹(CO)_mO-(A¹O)_n-R² (b1)

< 5 > the detergent composition for fiber products as < 4 > wherein, in the general formula (b1), R¹The number of carbon atoms of (a) is preferably 12 or more, more preferably 12.5 or more, further preferably 13.0 or more, and preferably 16 or less, more preferably 15 or less.

< 6 > such as < 5 > or < 6 >, wherein, in the general formula (b1), R¹The aliphatic hydrocarbon group of (2) is a group selected from an aliphatic alkyl group and an aliphatic alkenyl group.

< 7 > the detergent composition for fiber products as described in any of < 4 > to < 6 >, wherein, in the general formula (b1), A¹The O group is a group containing an ethyleneoxy group.

< 8 > the detergent composition for fiber products, wherein n in the general formula (b1) is preferably 6.5 or more, more preferably 7 or more, further preferably 8 or more, further more preferably 9 or more, further more preferably 10 or more, further more preferably 12 or more, and is 50 or less, preferably 45 or less, more preferably 40 or less, further preferably 35 or less, further more preferably 26 or less, further more preferably 24 or less.

The detergent composition for fiber products of < 9 > is, for example, any one of < 1 > to < 8 >, wherein the component (A) is an internal olefin sulfonate having 5 to 24 carbon atoms, the number of carbon atoms of which is 15 to 24 inclusive, and the sulfonic acid group is present at the 5-position, and the number of carbon atoms of which is 15 to 24 inclusive, is 5 to 60% by mass.

< 10 > the detergent composition for fiber products < 9 >, wherein the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 5-position or more in the component (a) is more preferably 57% by mass, still more preferably 54% by mass, still more preferably 50% by mass, still more preferably 46% by mass, still more preferably 42% by mass, still more preferably 35% by mass, and preferably 10% by mass or more.

< 11 > the detergent composition for textile articles according to any one of < 1 > to < 10 >, wherein the mass ratio of the component (B) to the component (A) (B)/(A) is 0.05 or more and 9 or less.

< 12 > the detergent composition for fiber products < 11 >, wherein the mass ratio (B)/(a) of the content of the component (B) to the content of the component (a) is preferably 0.08 or more, more preferably 0.1 or more, further preferably 0.15 or more, further more preferably 0.2 or more, further more preferably 0.25 or more, further more preferably 0.3 or more, further more preferably 0.35 or more, further more preferably 0.40 or more, and preferably 8 or less, further preferably 7 or less, further more preferably 6 or less, further more preferably 5 or less.

< 13 > the detergent composition for textile products, wherein the component (A) is at least 1 selected from the following components (a1) and (a2), the mass ratio of the component (a2) to the component (a1) (a2)/(a1) is 0 to 1,

< 14 > the detergent composition for textile products < 13 >, wherein the mass ratio (a2)/(a1) of the component (a2) to the component (a1) is 1 or less, preferably 0.95 or less, more preferably 0.9 or less, still more preferably 0.8 or less, still more preferably 0.7 or less, still more preferably 0.6 or less, still more preferably 0.5 or less, still more preferably 0.4 or less, still more preferably 0.3 or less, still more preferably 0.2 or less, still more preferably 0.1 or less, still more preferably 0.05 or less, and still more preferably 0.

The detergent composition for fiber products, wherein the total content of the component (A) and the component (B) in all the surfactants in the detergent composition for fiber products is 60 to 100 mass%.

< 16 > the detergent composition for fiber products < 15 >, wherein the total of the content of the component (A) and the content of the component (B) in the total surfactant in the detergent composition for fiber products is preferably 70% by mass or more, more preferably 80% by mass or more, further more preferably 90% by mass or more, further more preferably 95% by mass or more, and 100% by mass or less, or 100% by mass.

The detergent composition for fiber products of < 17 > as described in any one of < 1 > to < 16 > further contains water.

< 18 > a method for cleaning a fiber product, wherein the fiber product is cleaned with a cleaning liquid containing the following component (A), component (B) and water, and the hardness of the cleaning liquid exceeds 0 DEG dH,

< 19 > the method for cleaning a fiber product as < 18 >, wherein the hardness of the cleaning liquid is preferably 0.5 ° dH or more, more preferably 1 ° dH or more, further preferably 2 ° dH or more, further more preferably 3 ° dH or more, and preferably 20 ° dH or less, more preferably 10 ° dH or less, further preferably 8 ° dH or less, further more preferably 6 ° dH or less, as measured by a german durometer.

< 20 > a process for producing a detergent composition for fiber products, which comprises mixing the following component (A) with the following component (B),

Examples

< formulation >

In examples and comparative examples, and blending examples and comparative blending examples, the following components were used.

Synthesis of [ (A) component ]

The internal olefins A to C which become the raw materials of the component (A) were synthesized in the following manner.

Synthesis of C16 internal olefins A to C (production examples A to C)

Into a flask equipped with a stirrer were charged 7000g (28.9 mol) of 1-hexadecanol (product name: Kalcol 6098, manufactured by Kao corporation) and 700g (10 mass% based on the raw material alcohol) of gamma-alumina (STREM Chemicals, Inc.) as a solid acid catalyst, and the reaction was carried out while changing the reaction time according to production examples A to C while introducing nitrogen gas (7000mL/min.) into the system at 280 ℃ under stirring. The obtained crude internal olefin was transferred to a distillation flask and distilled at 160 ℃ C/4.0 mmHg at 136-. The double bond distribution of the internal olefins obtained is shown in table 1.

[ Table 1]

The double bond distribution of the internal olefin was determined by gas chromatography (hereinafter abbreviated as GC). Specifically, after dimethyl disulfide is reacted with an internal olefin to produce a disulfide derivative, each component is separated by GC. As a result, the distribution of the double bonds of the internal olefins was determined from the peak areas of the respective internal olefins. Further, in the olefins having 16 carbon atoms, the internal olefins having a double bond at the 7-position and the internal olefins having a double bond at the 8-position cannot be structurally distinguished from each other, and in the case of sulfonation, for the sake of convenience, values obtained by dividing the amount of internal olefins having a double bond at the 7-position by 2 are shown in the columns at the 7-position and 8-position.

The apparatus and analysis conditions used for the measurement are as follows. GC apparatus "HP 6890" (manufactured by HEWLETT PACKARD Co.), column "Ultra-Alloy-1 HT capillary column" (30 m.times.250. mu.m.times.0.15. mu.m, manufactured by Frontier Laboratories Ltd.), detector (hydrogen Flame Ionization Detector (FID)), injection temperature 300 ℃, detector temperature 350 ℃, He flow 4.6 mL/min

Synthesis of Components (a-1) to (a-10)

The internal olefins a to C obtained by the production examples a to C were subjected to sulfonation with sulfur trioxide gas by using a membrane sulfonation reactor having a jacket pipe on the outside thereof and passing cooling water of 20 ℃ through the jacket pipe on the outside of the reactor. SO in sulfonation reaction₃The molar ratio/internal olefin was set to 1.09. The obtained sulfonated product was added to an alkaline aqueous solution prepared with sodium hydroxide in an amount 1.5 times by mole with respect to the theoretical acid value, and stirred while stirringNeutralization was carried out at 30 ℃ for 1 hour. Hydrolysis was carried out by heating the neutralized product at 160 ℃ for 1 hour in an autoclave to obtain a crude product of sodium internal olefin sulfonate having 16 carbon atoms. 300g of the crude product was transferred to a separatory funnel, 300mL of ethanol was added, and 300mL of petroleum ether was added every 1 time to extract and remove oil-soluble impurities. At this time, the inorganic compound (the main component is mirabilite) precipitated at the oil-water interface by the addition of ethanol is also separated and removed from the aqueous phase by the oil-water separation operation. This extraction removal operation was performed 3 times. The aqueous phase was evaporated to dryness to obtain components (a-1), (a-4) and (a-10), respectively, which were sodium internal olefin sulfonates having 16 carbon atoms. Here, the internal olefin sulfonate obtained from the internal olefin A as a raw material is component (a-1), the internal olefin sulfonate obtained from the internal olefin B as a raw material is component (a-4), and the internal olefin sulfonate obtained from the internal olefin C as a raw material is component (a-10).

The positional distribution of the sulfonic acid group-bonded carbons of the obtained component (a-1), component (a-4), and component (a-10) is shown in table 2.

The content ratio of the sulfonic acid group-bonded internal olefin sulfonate is determined by high performance liquid chromatography/mass spectrometry (HPLC-MS). Specifically, the hydroxyl group bonded with the sulfonic acid group was separated by High Performance Liquid Chromatography (HPLC), and identified by a Mass Spectrometer (MS). As a result, the respective ratios were determined from the HPLC-MS peak areas. In the present specification, the respective proportions obtained from the peak areas are calculated as mass proportions.

The apparatus and conditions used for the measurement are as follows. HPLC apparatus "LC-20 ASXR" (manufactured by Shimadzu Corporation), column "ODS Hypersil (registered trademark)" (4.6X 250mM, particle size: 3 μm, manufactured by Thermo Fisher Scientific Corporation), sample preparation (1000-fold dilution with methanol), eluent A (aqueous solution to which 10mM ammonium acetate was added), eluent B (10 mM ammonium acetate was added, methacrylonitrile/water 95/5(v/v) solution), gradient (0 minute (A/B60/40) → 15.1-20 minutes (30/70) → 20.1-30 minutes (60/40), MS apparatus "LCMS-2020" (manufactured by Shimadzu Corporation), ESI detection (anion detection m/z: 321.10 (component (A) having 16 carbon atoms), column temperature (40 ℃), flow rate (0.5mL/min), and, Injection capacity (5 μ L)

[ Table 2]

Next, component (a-2) and component (a-3) are prepared by mixing component (a-1) with component (a-4). Further, components (a-5) to (a-9) are prepared by mixing component (a-4) with component (a-10).

The distribution of double bonds of internal olefins in the raw materials to be the obtained components (a-1) to (a-10) is shown in Table 3.

The positional distribution of the carbons to which the sulfonic acid groups of the obtained components (a-1) to (a-10) were bonded is shown in Table 4.

[ Table 3]

[ Table 4]

[ (B) component ]

(b-1): polyoxyalkylene lauryl ether (a compound obtained by adding an ethyleneoxy group in an amount of 9 moles on average to 1 mole of lauryl alcohol, then adding an propyleneoxy group in an amount of 2 moles on average, and then adding an ethyleneoxy group in an amount of 9 moles on average, wherein HLB is 14.5, and in general formula (b1), R is represented by¹: lauryl group, m: 0. a. the¹O: ethyleneoxy and propyleneoxy, n: 20. r²: a compound of a hydrogen atom)

(b-2): polyoxyalkylene lauryl ether (average number of moles of oxyethylene groups added is 10 moles, HLB is 14.0, and in general formula (b1), R¹: lauryl group, m: 0. a. the¹O: ethyleneoxy group, n: 10. r²: a compound of a hydrogen atom)

(b-3): polyoxyethylene alkyl groupEther (average number of moles of oxyethylene groups added 6 moles, HLB 12.1, in general formula (b1), R¹: is a mixed alkyl of lauryl and myristyl, the ratio of the mass of lauryl to the mass of myristyl, i.e. lauryl/myristyl 9/1, m: 0. a. the¹O: ethyleneoxy group, n: 6. r²: a compound of a hydrogen atom)

(b-4): polyoxyethylene alkyl ether (average number of moles of oxyethylene groups added is 5 moles, HLB is 10.7, and in general formula (b1), R is¹: is a mixed alkyl of lauryl and myristyl, the ratio of the mass of lauryl to the mass of myristyl, i.e. lauryl/myristyl 9/1, m: 0. a. the¹O: ethyleneoxy group, n: 5. r²: a compound of a hydrogen atom)

[ (B') component ] (comparative component for B component)

(b' -1): polyoxyethylene lauryl ether (average number of moles of oxyethylene groups added is 3 moles, HLB is 8.3, and in general formula (b1), R is¹: lauryl group, m: 0. a. the¹O: ethyleneoxy group, n: 3. r²: a compound of a hydrogen atom)

[ optional Components ]

[ (C) ingredient ]

(c-1): sodium alkyl benzene sulfonate (alkyl composition: C10/C11/C12/C13 ═ 11/29/34/26 (mass ratio), mass average carbon number ═ 17.75)

[ Water ]

Ion exchange water

< preparation of detergent composition for fiber product >

Using the above compounding ingredients, detergent compositions for fiber products shown in tables 5 to 6 were prepared, and the following items were evaluated. The results are shown in tables 5 to 6.

The methods for producing the detergent compositions for fibers shown in tables 5 to 6 were specifically produced as follows. A5 cm stirring piece (sticrer piece) made of Teflon (registered trade name) was put into a glass beaker having a capacity of 200mL, and the weight was measured. Then, 80g of ion-exchanged water at 20 ℃ was charged, and the top surface of the beaker was sealed with Saran Wrap (registered trademark). The beaker containing the contents was placed in a water bath of 60 ℃ equipped with a magnetic stirrer, and stirred at 100r/min for 30 minutes at a temperature of water in the water bath of 60. + -. 2 ℃. Next, the water in the water bath was replaced with tap water at 5 ℃ and the mixture was cooled until the temperature of the mixture in the beaker became 20 ℃. Subsequently, Saran Wrap (registered trademark) was removed, ion-exchanged water was added so that the weight of the contents became 100g, and the mixture was stirred at 100r/min for 30 seconds again to obtain detergent compositions for fiber products as shown in tables 5 to 6.

In addition, in table 6, blending examples 1 to 6 and comparative blending example 1 were prepared by changing the mass ratio of the content of component (a) to the content of component (B) with the total of the content of component (a) and the content of component (B) in the detergent composition for fiber products set to 10 mass%. Each blend example was prepared by changing the component (A) to each of the components (a-1) to (a-10). Component (B) was used in blending examples 1 to 3, (B-1) in blending example 4, (B-3) in blending example 5 and (B-4) in blending example 6.

< evaluation method >

[ production of fiber product for evaluation ]

(1) Production of fiber product for evaluation of adsorption ratio of surfactant

After washing cotton knit goods 1.7kg (manufactured by colordye corporation, pure cotton knitted unripened (not mercerized) and cotton 100%) by a standard procedure of a full-automatic washing machine (NA-F702P manufactured by National) 2 times cumulatively (Emulgen 108 (manufactured by kao corporation) 4.7g, water amount 47L, washing 9 minutes, rinsing 2 times, dehydrating for 3 minutes at the time of cleaning), washing with water 3 times cumulatively (water amount 47L, washing 9 minutes, rinsing 2 times, dehydrating for 3 minutes) and drying at 23 ℃ and 45% RH for 24 hours. Thereafter, the cut pieces were cut into a size of 6cm × 6 cm.

(2) Preparation of fiber product for evaluation of cleaning efficiency

Preparation of model sebum Artificial stained cloth

A model sebum artificial stain having the following composition was attached to a cloth (Cotton 2003 (manufactured by Takara Shuzo)) to prepare a model sebumArtificially polluting cloth. The adhesion of the model sebum artificial stain to the cloth was performed by printing the artificial stain on the cloth using a gravure roll coater. The step of preparing the artificial contaminated cloth with model sebum by adhering the artificial contaminated liquid with model sebum to the cloth was carried out in a gravure roll unit capacity of 58cm³/m²The coating speed was 1.0m/min, the drying temperature was 100 ℃ and the drying time was 1 min. Thereafter, the cut pieces were cut into a size of 6cm × 6 cm.

﹡ composition of artificial sebum contaminated liquid: 0.4 mass% of lauric acid, 3.1 mass% of myristic acid, 2.3 mass% of pentadecanoic acid, 6.2 mass% of palmitic acid, 0.4 mass% of heptadecanoic acid, 1.6 mass% of stearic acid, 7.8 mass% of oleic acid, 13.0 mass% of glycerol trioleate, 2.2 mass% of n-hexadecyl palmitate, 6.5 mass% of squalene, 1.9 mass% of protein lecithin liquid crystal, 8.1 mass% of evergreen, 0.01 mass% of carbon black, and the balance of water (total 100 mass%)

[ cleaning test ]

(1) Cleaning test 1

The cleaning operation was performed using a Terg-O-Tometer (manufactured by Upper island fabrication). The water used for cleaning was obtained by adding calcium chloride and magnesium chloride to ion-exchanged water at a mass ratio of 8:2 to adjust the hardness to 4 ° dH. The cleansing liquid was obtained by mixing the cleansing water with the total amount of the components (a), (B), (C) and (B ') in the cleansing composition for fiber products described in table 5 or 6 so that the concentration of the total amount of the components (a), (B), (C) and (B') in the cleansing liquid was 167 mg/kg. In a 1-liter stainless steel beaker for the cleaning test, 0.6L of cleaning solution and 5 pieces of the fiber product for evaluation of the adsorption rate of the surfactant were put. The bath ratio was adjusted to 15 by the above-mentioned fiber product for evaluation of adsorption rate. The temperature of the cleaning liquid was 20 ℃. The fibers for evaluation were cleaned using a Terg-O-Tometer at 85rpm for 10 minutes. After cleaning, the mixture was dehydrated and dried at 23 ℃ and 45% RH for 24 hours.

(2) Cleaning test 2

The cleaning operation was performed using a Terg-O-Tometer (manufactured by Upper island fabrication). The water used for cleaning was obtained by adding calcium chloride and magnesium chloride to ion-exchanged water at a mass ratio of 8:2 to adjust the hardness to 4 ° dH. The cleansing liquid was obtained by mixing the cleansing water with the total amount of the components (a), (B), (C) and (B ') in the cleansing composition for fiber products described in table 5 or 6 so that the concentration of the total amount of the components (a), (B), (C) and (B') in the cleansing liquid was 167 mg/kg. In a 1-liter stainless steel beaker for the cleaning test, 0.6L of cleaning solution and 5 pieces of the fiber product for evaluation of the above cleaning ratio were put. The bath ratio was adjusted to 15 using the fiber product for evaluation of cleaning rate, and the temperature of the cleaning liquid was 20 ℃. The fibers for evaluation were cleaned using a Terg-O-Tometer at 85rpm for 10 minutes. After cleaning, dewatering and drying by using an ironing press.

[ quantification of the amount of adsorption of surfactant to fiber product ]

2 pieces of the fiber product for evaluation of the surfactant adsorption ratio after the cleaning test 1 were taken out, sealed in a No.7 screw tube, and the weight of the cloth was measured. To this solution, 40mL of a methanol/chloroform solution (methanol: chloroform: 1 (volume ratio)) was added, and ultrasonic treatment was performed for 50 minutes using an ultrasonic cleaner. The extract was diluted 20 times to obtain a solution for measurement. Subsequently, the component (a), the component (B), and the component (C) were diluted with a methanol/chloroform solution (methanol: chloroform: 1 (volume ratio)) to prepare solutions for calibration curves of 0.1 μ g/mL, 0.5 μ g/mL, 1 μ g/mL, and 5 μ g/mL. The amount of the surfactant in the measurement solution was determined by a liquid chromatography mass spectrometer (hereinafter, referred to as an LCMS apparatus), and the amount of the active agent adsorbed to the fiber product was determined from the solution based on a calibration curve.

LCMS apparatus: LCMS2020 available from Shimadzu corporation

Eluent a: 10mmol/L ammonium acetate in distilled water

Eluent B: 10mmol/L of ammonium acetate in methanol

Gradient conditions: eluent a/B ═ 1:1(0 min) → eluent B (2-5 min) → eluent a/eluent B ═ 1/1(5.1 min-8 min), flow rates: 0.6mL/min, 5. mu.l of sample injection amount, 40 ℃ of column temperature

The adsorption rate of the surfactant to the fiber product was determined according to the following formula. The results are shown in table 5.

The adsorption rate of the total surfactant was 100 × { (total weight of the surfactant adsorbed to 2 pieces of the fiber used for measurement of adsorption amount) × (total weight of the fiber used for cleaning test 1)/(weight of 2 pieces of the fiber used for measurement of adsorption amount) }/(total weight of the surfactant used for preparation of the cleaning solution)

[ evaluation method of cleaning efficiency ]

The cleaning ratio of the evaluation fiber product obtained in the above cleaning test 2 was measured by the following method, and the average of 5 pieces was obtained. The results are shown in table 6.

The reflectance at 550nm before and after the cleaning was measured by a colorimeter (Z-300A manufactured by Nippon Denshoku Kogyo Co., Ltd.), and the cleaning ratio (%) was determined by the following equation. The values in table 6 are the average values of the cleaning rates of 5 blocks.

Cleaning ratio (%) < 100 × [ (reflectance after cleaning-reflectance before cleaning)/(reflectance of original cloth-reflectance before cleaning) ]

[ Table 5]

(examination)

In table 5, if comparative example 4 is compared with the examples, it is understood that: by using the component (a) of the present invention as an anionic surfactant, the amount of a surfactant adsorbed on a textile after cleaning is reduced as compared with an alkylbenzene sulfonate which is a general cleaning component. Further, it is found that by using the component (a) in combination with the component (B), the amount of the surfactant adsorbed on the fiber product after cleaning is reduced. It was also found that even when the component (a) of the present invention was used, the adsorption rate was not decreased when a surfactant other than the component (B) of the present invention was used.

[ Table 6]

(examination)

In table 6, in the case where only the component (a) is present as in comparative formulation example 1, if the content of the olefin having the double bond position at 5 or more in the raw material olefin of the component (a) is changed, the cleanability is changed. However, in blending examples 1 to 6 in which the component (A) and the component (B) were used in combination, it was found that the content of the olefin in which the position of the double bond in the raw material olefin of the component (A) was present at 5 or more positions was large in the range of the content in which the cleaning ratio was not changed. Further, it is found that the content range of the content in which the cleaning ratio does not change among the content of the olefin having the double bond position at 5 or more in the raw material olefin of the component (a) becomes larger as the content ratio of the component (B) becomes higher.

Claims

1. A detergent composition for fiber products, wherein,

comprises the following components (A) and (B),

(A) the components: an internal olefin sulfonate having 15 to 24 carbon atoms;

(B) the components: a nonionic surfactant having an HLB of more than 10.5 and not more than 19,

the component (A) contains 29.9 to 60 mass% of an internal olefin sulfonate having 15 to 24 carbon atoms in which a sulfonic acid group is present at the 5-position, the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 1-position being 0.01 to 10 mass%, the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 2-position being 10 to 24.1 mass%, the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 3-position being 19.9 mass% or less, and the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 4-position being 24.6 mass% or less,

(B) a nonionic surfactant represented by the following general formula (b1),

R¹(CO)_mO-(A¹O)_n-R² (b1)

in the formula, R¹Is an aliphatic hydrocarbon group having 9 to 18 carbon atoms, R²Is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, A¹The O group is 1 or more selected from the group consisting of an ethyleneoxy group and a propyleneoxy group, and n is an average addition mole number and is a number of 6 to 50.

2. The detergent composition for textile articles according to claim 1, wherein,

(B) the component (A) is a nonionic surfactant containing a polyoxyethylene group and having an HLB of more than 10.5 and not more than 19.

3. The detergent composition for textile articles according to claim 2, wherein,

(B) the HLB of the component (A) is 12 to 19 inclusive.

4. The detergent composition for textile articles according to claim 1, wherein,

in the general formula (b1), R¹Has 12 to 16 carbon atoms.

5. The detergent composition for fiber products according to claim 1 or 4, wherein,

in the general formula (b1), R¹The aliphatic hydrocarbon group of (2) is a group selected from an aliphatic alkyl group and an aliphatic alkenyl group.

6. The detergent composition for fiber products according to claim 1 or 4, wherein,

in the general formula (b1), A¹The O group is a group containing an ethyleneoxy group.

7. The detergent composition for fiber products according to claim 1 or 4, wherein,

in the general formula (b1), n is 6.5 or more and 35 or less.

8. The detergent composition for fiber products according to claim 1 or 4, wherein,

in the general formula (b1), n is 7 or more and 24 or less.

9. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(A) the content of the internal olefin sulfonate having 15 to 24 carbon atoms with the sulfonic acid group being present at the 5-position in the component (A) is 57 mass% or less.

10. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(A) the content of the internal olefin sulfonate having 15 to 24 carbon atoms with the sulfonic acid group being present at the 5-position in the component (A) is 46 mass% or less.

11. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(A) the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 2-position in the component (A) is 15 mass% or more.

12. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(A) the content of the internal olefin sulfonate having 15 to 24 carbon atoms in which the sulfonic acid group is present at the 2-position in the component (A) is 20 mass% or more.

13. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(B) the mass ratio (B)/(A) of the component (A) to the component (B) is 0.05 to 9 inclusive.

14. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(B) the mass ratio (B)/(A) of the content of the component (A) to the content of the component (A) is 0.1 to 5.

15. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(B) the mass ratio (B)/(A) of the content of the component (A) to the content of the component (B) is 0.2 to 5.

16. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

(A) the component (a) is at least 1 selected from the following components (a1) and (a2), the mass ratio of the component (a2) to the component (a1) (a2)/(a1) is 0 to 1,

(a1) the components: an internal olefin sulfonate having 15 to 16 carbon atoms;

(a2) the components: an internal olefin sulfonate having 17 to 24 carbon atoms,

(a1) the component (B) contains an internal olefin sulfonate having 15 to 16 carbon atoms in which a sulfonic acid group is present at the 5-position or higher,

(a2) the component (B) contains an internal olefin sulfonate having 17 to 24 carbon atoms in which a sulfonic acid group is present at the 5-position.

17. The detergent composition for fiber products according to claim 16, wherein,

(a2) the mass ratio of component (a2)/(a1) to component (a1) is 0 to 0.3.

18. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

the total content of the component (A) and the component (B) in the total surfactant in the detergent composition for textile products is 60 to 100 mass%.

19. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

the total content of the component (A) and the component (B) in the total surfactant in the detergent composition for textile products is 80 to 100 mass%.

20. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

further comprising water.

21. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

the total content of the content of component (A) and the content of component (B) in the detergent composition for textile products is 4 to 60 mass%.

22. The detergent composition for fiber products according to any one of claims 1 to 4, wherein,

the total content of the content of component (A) and the content of component (B) in the detergent composition for textile products is 7 to 50 mass%.

23. A method for cleaning a fibrous article, wherein,

a method for cleaning a fiber product with a cleaning solution containing a component (A), a component (B) and water, wherein the hardness of the cleaning solution exceeds 0 DEG dH,

(A) the components: an internal olefin sulfonate having 15 to 24 carbon atoms;

(B) a nonionic surfactant represented by the following general formula (b1),

R¹(CO)_mO-(A¹O)_n-R² (b1)

24. The method of cleaning a fibrous article according to claim 23,

25. The method of cleaning a fibrous article according to claim 23,

in the general formula (b1), R¹Has 12 to 16 carbon atoms.

26. The method of cleaning a fibrous article according to claim 23 or 25,

27. The method of cleaning a fibrous article according to claim 23 or 25,

28. The method of cleaning a fibrous article according to claim 23 or 25,

in the general formula (b1), n is 6.5 or more and 35 or less.

29. The method of cleaning a fibrous article according to claim 23 or 25,

in the general formula (b1), n is 7 or more and 24 or less.

30. A method of cleaning a fibrous article according to any of claims 23 to 25,

31. A method of cleaning a fibrous article according to any of claims 23 to 25,

32. A method of cleaning a fibrous article according to any of claims 23 to 25,

33. A method of cleaning a fibrous article according to any of claims 23 to 25,

the mass ratio (B)/(A) of the component (B) to the component (A) in the cleaning liquid is 0.05 to 9.

34. A method of cleaning a fibrous article according to any of claims 23 to 25,

the mass ratio (B)/(A) of the content of the component (B) to the content of the component (A) in the cleaning liquid is 0.1 to 5.

35. A method of cleaning a fibrous article according to any of claims 23 to 25,

the mass ratio (B)/(A) of the content of the component (B) to the content of the component (A) in the cleaning liquid is 0.2 to 5.

36. A method of cleaning a fibrous article according to any of claims 23 to 25,

(A) the component (a) is selected from the following (a1) component and (a2) component, the mass ratio of the (a2) component to the (a1) component in the cleaning solution (a2)/(a1) is 0 to 1,

(a1) the components: an internal olefin sulfonate having 15 to 16 carbon atoms;

(a2) the components: an internal olefin sulfonate having 17 to 24 carbon atoms,

37. The method of cleaning a fibrous article according to claim 36,

the mass ratio (a2)/(a1) of the component (a2) to the component (a1) in the cleaning liquid is 0 to 0.3.

38. A method of cleaning a fibrous article according to any of claims 23 to 25,

the total of the content of the component (A) and the content of the component (B) in the entire surfactant in the cleaning liquid is 60 mass% or more and 100 mass% or less.

39. A method of cleaning a fibrous article according to any of claims 23 to 25,

the total of the content of the component (A) and the content of the component (B) in the total surfactant in the cleaning liquid is 80 mass% or more and 100 mass% or less.

40. A method of cleaning a fibrous article according to any of claims 23 to 25,

the hardness of the cleaning liquid is 0.5 DEG dH or more and 20 DEG dH or less in terms of German hardness.

41. A method of cleaning a fibrous article according to any of claims 23 to 25,

the content of the component (a) in the cleaning liquid is 0.005 mass% or more and 1.0 mass% or less, and the content of the component (B) in the cleaning liquid is 0.001 mass% or more and 5.0 mass% or less.

42. A process for producing a detergent composition for textile products, wherein,

mixing the following component (A) with the following component (B),

(A) the components: an internal olefin sulfonate having 15 to 24 carbon atoms;

(B) a nonionic surfactant represented by the following general formula (b1),

R¹(CO)_mO-(A¹O)_n-R² (b1)

in the formula, R¹Is an aliphatic hydrocarbon group having 9 to 18 carbon atoms, R²Is a hydrogen atom or a methyl group, CO is a carbonyl group, m is a number of 0 or 1, A¹O group is more than 1 selected from ethyleneoxy and propyleneoxy, and n is flatA number of average addition mols of 6 to 50 inclusive.